N-polyhalovinylthiocarboxamides

ABSTRACT

N-polyhalovinylthiocarboxamides of the formula: WHERE R is an aliphatic hydrocarbon radical of one to 10 carbon atoms which has zero to about three halogen substituents of atomic number 17 to 35, R&#39;&#39; is hydrogen or alkyl of one to four carbon atoms with the proviso that R and R&#39;&#39; may be joined to form a linear alkylene radical of three to five carbon atoms which is bound to the carbonyl and nitrogen to form a ring, X is halogen of atomic number 17 to 35 and a is two or three. These carboxamides are fungicidal, algicidal and nematocidal.

United States Patent Brown [4 1 July 25, 1972 [54]N-POLYHALOVINYLTHIOCARBOXA- MIDES [72] Inventor:

[73] Assignee:

Melancthon S. Brown, Berkeley, Calif.

Chevron Research Company, San Francisco, Calif.

[22] Filed: April 30, 1970 [21] Appl. No.: 33,879

Related 0.5. Application Data [63] Continuation-impart of Ser. Nos.810,368, March 25, 1969, abandoned, and Ser. No. 748,642, June 30, 1968,abandoned, Ser. No. 810,368, which is a continuation-in-part of Ser. No.748,642, and Ser. No. 704,555, Feb. 12, 1968, abandoned, Ser. No.748,642, which is a continuation-in-part of Ser. No. 704,555.

[52] [1.8. CI. ..260/239.3 R, 260/453 R, 260/561 S, 260/559 T, 260/558S, 260/557, 260/326.5 S,

[51] Int. Cl. ..C02d 41/06 [58] Field of Search ..260/239.3, 293.4,293.46, 325.5 S, 260/557, 558 S, 559 T, 561 S, 453

[5 6] References Cited UNITED STATES PATENTS 3,344,153 9/1967 Kuhle eta1 ..260/347.2

FOREIGN PATENTS OR APPLICATIONS 1,494,221 7/1967 France ..260/559976,957 12/1964 Great Britain ..260/239.3

Primary Examiner-Henry R. Jiles Assistant ExaminerRobert T. BondAttorney-J. A. Buchanan, .112, G. F. Magdeburger, John Stoner, Jr. andRaymond Owuang [5 7] ABSTRACT N-polyhalovinylthiocarboxamides of theformula:

9 Claims, No Drawings N-POLYHALOVINYL'I'I'IIOCARBOXAMIDES CROSSREFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of application Ser. No. 810,368, filed Mar. 25,1969, now abandoned and application Ser. No. 748,642, filed June 30,1968, now abandoned. Application Serial No. 810,368 is acontinuation-in-part of application Ser. No. 748,642 and applicationSer. No. 704,555, filed Feb. 12, 1968, now abandoned. Application Ser.No. 748,642 is a continuation-in-part of application Ser. No. 704,555.Related application Ser. No. 810,377 was filed Mar. 25, 1969 and is nowabandoned.

FlELD OF INVENTION This invention concernsN-polyhalovinylthiocarboxamides and their use as pesticides, especiallyas nematocides.

INVENTION DESCRIPTION The novel carboxamides of the present inventionmay be represented by the formula wherein R is an aliphatic hydrocarbonradical of one to l carbon atoms which has zero to three halogensubstituents of atomic number 17 to 35, i.e., R is alkyl of one to l0carbon atoms, alkenyl of two to carbon atoms, alkynyl of two to 10carbon atoms, haloalkyl of one to 10 carbon atoms and one to threehalogen atoms of atomic number 17 to 35, cycloalkyl of three to 10carbon atoms, cycloalkyl of three to 10 carbon atoms, preferablycyclohexyl, substituted with one to three halogen atoms of atomic number17 to 35, or cycloalkenyl of three to ten carbon atoms; R is hydrogen oralkyl of one to four carbon atoms with the proviso that R and R may bejoined to form a linear alkylene radical of 3 to 5 carbon atoms which isbound to the carbonyl and nitrogen to form a ring; X is halogen ofatomic number 17 to 35; and a is two or three.

Preferably X is chlorine; a is three; R is an aliphatic hydrocarbonradical of one to eight carbon atoms which is free of aliphaticunsaturation and has zero to three halogen substituents, more preferablyzero to two chloro substituents, i.e., R is alkyl of one to eight carbonatoms, haloalkyl of one to eight carbon atoms and one to three halogenatoms of atomic number 17 to 35, more preferably one to two chlorineatoms, cycloalkyl of three to eight carbon atoms, or cycloalkyl of threeto eight carbon atoms substituted with one to three halogen atoms ofatomic number 17 to 35, more preferably one to two chlorine atoms; and Ris hydrogen or alkyl of one to two carbon atoms.

The carboxamides in which R and R are joined to form a ring with thecarbonyl and nitrogen may alternatively be represented by the formulawherein R is linear alkylene of three to five carbon atoms and X and aare as defined previously.

Representative polyhalovinyl groups which .C,X,,H may represent aretrichlorovinyl, 1,2-dichlorovinyl, 2,2-dichlorovinyl, tribromovinyl,2,2-dibromovinyl, 1,2-dibromovinyl, 2- bromo-2-chlorovinyl and the like.

Organic groups which R may represent are alkyl, alkenyl, alkynyl,cycloalkyl and cycloalltenyl. Specific examples of such groups aremethyl, ethyl, isopropyl, n-butyl, propenyl, propynyl, sec.butyl, amyl,hexyl, octyl, decyl, 3-methylarnyl, cyclobutyl, cyclohexyl, cyclooctyland the like. Halo-substituted radicals which R may represent includechloroalkyl, bromoalkyl, chlorocycloalkyl and bromocycloalkyl. Specificexamples of such halo-substituted radicals are chloromethyl,2-chloroethyl, 3-chloropropyl, 4-chloroamyl, 6-chlorohexyl,

dichloropropionamide,

p-chloro-cyclohexyl, 2,6-dichlorocyclohexyl, cyclohexyl andp-bromocyclohexyl.

Alkyl radicals which R may represent include methyl, ethyl, n-propyl,isopropyl, n-butyl and isobutyl. Alkylene radicals which R and R takentogether or R may represent are propylene, butylene and amylene.

Typical carboxamides represented by the above formulas areN-trichlorovinylthioacetamide, N-tribromovinylthioactamide,N-l,2-dichlorovinylthioacetarnine, N-2-bromo-2-chlorovinylthioacetamide, N-methyl-N-l ,2-dibromovinylthioacetamine,N-ethyl-N-trichlorovinylthioacetamide, N-isobutyl-N-2-bromo-2-chlorovinylthioacetamide, N-tribromovinylthiochloroacetamide, N-ethyl-N-l-chloro-Z-bromovinylthiobromoacetamide, N- l ,Z-dibromovinylthiopropionamide,N-2,2-dichlorovinylthiopropionamide,N-Z-bromo-2-chlorovinylthiopropionamide, N-methyl-N-trichlorovinylthiopropionamide, N-isopropyl-N- l chloro-Z-bromovinylthiopropionamide, N-n-butyl-N- l,2-dichlorovinylthiopropionamide, N-trichlorovinylthio-3,3-N-methyl-N-Z,2-dichlorovinylthio- 2,3-dibromopropionamide,N-butyl-N-l-chloro-2-bromovinylthiochloropropionamide,N-l,2-dichlorovinylthiobutyramide, N-lchloro-2-bromovinylthiobutyramide,N-propyl-N- l ,2-dibromovinylthiobutyramide, chlorovinylthiopentamide,N-trichlorovinylthio-B,4,5- trichloropentanamide,N-butyl-N-tribromovinylthiohexanamide,N-2-bromo-2-chlorovinylthio-S-bromohexanamide, N-ethyl-N-trichlorovinylthioheptanamide,N-2,2-dichlorovinylthio-6,7-dichloroheptanamide,N-trichlorovinylthiooctanamide,N-propyl-N-2,2-dichlorovinylthio-3,5,7-tribromooctanamide,N-trichlorovinylthiodecanamide, N-methyl-N-l,2- dibromovinylthiolO-chlorodecanamide, N-butyl-N- trichlorovinylthioundecanamide, N- lchloro-2-bromovinylthioundecanamide, N-trichlorovinylthioacrylamide, N-methyl-N-trichlorovinylthio3-chloroacrylamide, N-butyl-N-trichlorovinylthiocrotonamide, N-2,2-dichlorovinylthio-2-ethylacrylamide, N-trichlorovinylthio-3-hexenamide, N-trichlorovinylthio-3-decenamide, N-trichlorovinylthiopropiolamide,N-trichlorovinylthio-Lbutynamide, N-trichlorovinylthiocyclooctanecarboxamide, N-propyl-N-tribromovinylthio-3,4-dichlorocyclohexanecarboxamide, N-trichlorovinylthio-4-bromocyclohexanecarboxamide, N-methyl'N-lchloro-2-bromovinylthio-2-chlorocyclobutanecarboxamide,N-trichlorovinylthiocyclohexenecarboxam ide,N-butyl-N-Z-bromo-Z-chlorovinylthiocyclohexenecarboxamide,N-trichlorovinylthiopyrrolidone, N-tribromovinylthiopyrrolidone,N-lchloro-2-bromovinylthiopyrrolidone, N-trichlorovinylthiopiperidone,nylthiopiperidone, N-2-bromo-2-chlorovinylthiopiperidone,N-trichlorovinylthiocaprolactam, N-2,2-dichlorovi nylthiocaprolactam andN-l-chloro-Z-bromovinylthiocaprolactam.

The carboxamides of this invention may be prepared by2,6-dibromoreacting a sulfenyl halide with a primary or secondarycarboxamide or a lactam. This reaction is illustrated by the followingchemical equation:

N-methyl-N-2-bromo-2- I N- l ,Z-dibromoviln'reactions wherein R' is anorganic group, it is necessary to have a mild, basic halogen halideacceptor present. At least stoichiometric amounts of acceptor should beused. Soluble tertiary amines such as pyridine and trialkylamines, e.g.,triethylamine and tripropylamine are preferred. Acceptors which arestrong enough to react with the sulfenyl halide reactant should beavoided. I Carboxamides of this invention may also be prepared bydehydrohalogenating corresponding N-polyhaloalkylthiocarboxamides. Forinstance, N-(tetrachloroethylthio) carboxamides may bedehydrochlorinated to produce N-trichlorovinylthiocarboxamides. Thisdehydrohalo genation will normally becarried out at low temperatures,usually about to 40 C. and in the presence of solvents such as benzene,toluene, ether, methylene chloride, acetonitrile and chloroform. Milddehydrohalogenating agents such as tertiary amines (trialkyl amines,pyridine, etc.) or alkali metal carbonates will normally be employed.Triethylamine is a preferred agent.

EXAMPLES The following examples describe methods which may be used toprepare the carboxamides of this invention. These examples are notintended to limit the invention described herein. Percentages are byweight.

Example 1 g. of acetamide and 100 ml. dimethylfonnamide were placed in avessel cooled in an ice bath. g. of freshly distilledtrichlorovinylsulfenyl chloride was added slowly to this mixture. Afterthis addition, the vessel was removed from the ice bath and allowed tostand for one hour at ambient temperature. One liter of ice water wasthen added to the vessel causing a precipitate to form. The vessel'scontents were then filtered and washed with water and hexane. The solidwas then dissolved in methylene chloride and the solution was dried overM,SO After drying, the methylene chloride was stripped off leaving 1 lg. of N-tn'chlorovinylthioacetamide. This compound, a white solid,melted at 79-82C. Its S and Cl analyses were:

Calculated Found Cl 43.3 47.90 Example 2 'A solution of 4 g.-oftriethylamine in 20 ml. of benzene were added dropwise to a solution of10 g. of N- 1 l ,2,2-tetrachloro ethylthiochloroacetamide in 100 ml. ofbenzene. The reaction mixture was then refluxed for two hours and thencooled and filtered. The filtrate was-washed twice with saturated sodiumchloride'solution, dried over magnesium sulfate, filtered and stripped.N-trichlorovinylthiochloroacetamide was recrystalhad from hexane.Chemical analyses showed the following:

Calculated Found S b 12.55 l2.52 Cl 55.6 53.3

The melting point of the compound was 85-95 C.

Other'carboxarnides of this invention were prepared by the methoddescribed in Example 1. These carboxamides are listed in Table l.

UTlLlTY The N-polyhalovinylthiocarboxamides of this invention haveexhibited biological activity against a variety of organisms,particularly fungi, algae and nematodes. Their activities againstnematodes were unexpectedly better than those of the most closelyrelated known carboxamides, the N-polyhaloalkylthiocarboxamides. Also,many of them were significantly better fungicides and algicides than theknown carboxamides.

The nematocidal activities of the carboxamides of this invention andtheir superiority over corresponding N- polyhaloalkylthio compounds wereillustrated by testing representative amides of this invention andrepresentative N- polyhaloalkylthio compounds by the following method.

TABLE II.-NEMATOCIDAL ACTIVITY, PERCENT A 0.38 ml. portion of a threepercent acetone solution of the test compound was diluted with 1 ml.acetone. The resulting solution was homogenously mixed with 20 cc. ofvermiculite.

The treated vermiculite was then mixed homogenously with 750 g. of soil,dry weight basis, which was severely infested with free-living nematodes(mixed culture of Meloidogyne javanica and Meloidogyne incognita). Thismixing gave a concentration of approximately 15 parts of the testcompound per million parts of soil. This treated soil was stored forfour days at -75 F. It was then divided equally into three parts, eachof which was put into a separate pot and kept for another three days. Athree week old tomato (v. Bonny Best) seedling was then transplantedinto each pot and incubated for 13 daysN-2,2-dichlorovinylthiopyrrolidone TAB LE I Element analyses, percent 8Cl Melting point, Compound Calculated Found Calculated FoundN-trichlorovinylthiochloroacetamide 12. 55 12. 52 55. 6 53. 3 -90N-trichlorovinylthlopropionamide 13. 65 13. 62 45. 4 45. 60 80-83 N-trichlorovlnylthiocyclohexanecarboxamide ll. 06 11. 23 36. 8 36. 55146-149 N-trichlorovinylthio-n-butyramide 12. 87 12. 92 42. 8 42. 3065-68 N-trlchlorovinylthio-n-hexanamide 11. 57 11. 88 38. 42 38. 6246-50 N-trichlorovlnylthioisobutyramide ll. 8 12. 37 39. 3 41. 94 -100N-trichiorovinylthiotrimethylacetami 12. 16 12. 22 40. 46 39. 85 -128N-trichlorovinylthioeyclopropanecarboxamlde 12. 97 13. 12 43. 1 42. 7088-91 N -methyl-N-trichlorovinylthioacetamide 1 13. 62 13. 28 45. 3 44.6 Oil N-methyl-N-trichlorovinylthiobutyramide-. 12. 18 12. 38 40. 5 40.5 Oil N -trichlorovlnylthiopyrrolidone 12. 96 l3. 10 43. 1 41. .1 OilN-triehlorovinylthiocaprolactam 11. 64 11. 68 38. 7 38. 65 OilN-2,2-dichlorovinylthlopropionamide 16. 00 15. 72 35. 45 35. 18 83-85N-2,2-dichlorovinylthiotrimcthylacetamidc. 14. 01 13.98 3L 0!! 30. 0091H)! l5. 10 14:58 33. 50 32. 70 07-102 under greenhouse conditions.After this period they were removed and the soil was washed from theirroots. The nematocidal effectiveness of the test compound was determinedby observing each plant for signs of nematode invasion (number of gallsformed, stunting, etc.

The results of these tests, reported as the average of the threereplicates on a zero to 100 basis -zero indicating no effectiveness; 100indicating complete effectiveness are reported in Table ll.

As illustrated above, the carboxamides of this invention may be used tocontrol plant-parasitic nematodes by exposing them to a toxic amount ofthe carboxamide. Thus, these carboxamides will normally be applied tonematode-infested soil at dosages in the range of three to 40 lbs. peracre. They may be applied as liquid formulations by spraying orinjection. The liquid formulations of these carboxamides may besolutions, dispersions, or emulsions. Typical solvents which may be usedare aromatics such as xylene, toluene and benzene, ketones such ascyclohexanone and the like. These liquid formulations will usuallycontain a wetting agent to facilitate the carboxamides penetration intothe soil and generally enhance its effectiveness. They may also beapplied as solid formulations containing carriers such as soil, sawdust,clay and the like. When used as a solid, these carboxamides will usuallybe plowed into the soil. Following their application to the soil, thesoil will be watered to disperse the carboxamide below ground level.

Carboxamides of this invention are particularly useful for controllingmicrobiological organisms such as algae, bacteria, molds andoccasionally aquatic weeds which foul aqueous industrial efiluents andcooling streams, such as those occurring in the paper and foodprocessing industries. They may also be used to control such organismsin other aqueous bodies such as lakes, streams, canals, pools and thelike. When so used, a biocidal quantity of one or more of thecarboxamides of this invention is added to the aqueous growthenvironment of the organisms. Usually, this dosage will range betweenabout 0.1 and 50 ppm. In any given instance, the optimum dosage willdepend upon the particular organism and aqueous body involved. Forinstance, when used to control algae, these carboxamides will usually beemployed at concentrations of about 0.1 to ppm. In terms of pounds ofcarboxamide per acre of water one foot deep 0.] to ID ppm is equal toabout 0.3 to 30 lbs. per acre of water one foot deep. These carboxamidesmay be applied to the aqueous growth environments of such organisms asdispersible powders or in solution with water-miscible solvents.

Representative carboxamides of this invention were tested as algicidesby the following method.

An acetone solution of equal parts of carboxamide and a surfactant wasprepared. This solution was mixed with a nutrient broth in a quantitysufficient to give a concentration of 2 ppm. carboxamide. Four replicate150 ml. specimen cups were filled with this mixture. 350-400 mg. ofEuglena was added to each specimen cup and the cups were then placed inan environment chamber for incubation. The cups were observedperiodically for algae growth. The algicidal eflectiveness of thecarboxamide was determined based on a final observation of algae growthafter 10 days.

The results of these tests, reported as the average of the fourreplicates on a zero to l00 basis 0 indicating no effectiveness; 100indicating complete effectiveness are reported in Table II].

Comparative algicidal testing indicated the carboxamides of thisinvention were more effective than corresponding N-polyhaloalkylthiocarboxamides.

Carboxamides of this invention were also used to control fungi such asPythium ultimum, Rhizoctonia solam', Fusarium oxysporum, f. phaseoli,Helminthasporium sativum, Verlicillium aIbo-atrum, atrum, Moniliniafructicola and Alternaria solani and bacteria such as Erwinia caratovaraand Pseudomonas syringae When used as fungicides or bactericides, thecarboxamides of this invention will be formulated and applied infungicidal or bactericidal, as the case may be, amounts by conventionalart methods to fungi, bacteria or hosts which are subject to fungus orbacteria attack, especially vegetative hosts such as plants, plantseeds, paper and the like. They may be combined with inert liquids andsolid carriers as powders, solutions or dispersions for such use.

TABLE Ill Alglcldnl Compound vll'ootivvnussN-trlclilorovlnylLhincliloronootumldn I00N-U'lClllOI'OVlllylLlll0ll(ll\Lll.lIll(l(L 100N-trlohlorovlnyltliloproplmnmildn 100N-LI'llilllOl'OVlllylLlIlOUyUIOIWXILIlflClllbOXlllllldlL 8UN-t.rluhlorovlnyltlilolmtyrmnhlo. I00N-LrlolilorovlnyltlilolsoliuLyrnmlil 2H3N-trloh|orovlnylthlotrllnutliylnuutnl 100N-trlol|lorovliiyltlilooycIopropnnminrlioxnln11 I00N-tnothyl-N-trluhlorovluylLhionu-tumid 100N-triclilorovinylthiopyrrnlldono 100 N-trlcl1lorovliiyltlilocuprolnotnni 100 N-nicthyl-N-triohlorovinylbntyrnmidc 100 N-2,2-(1lclilorovinylthiotrimethylucetumldo 94 N -2,Z-dlchlorovinylthiopyrrolldono J0 Pesticidal formulations of thecarboxamides of this invention may also contain stabilizers, spreadingagents, sticking agents, fillers, other compatible pesticides and thelike.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in the light of the foregoingdisclosure and discussion, without departing from the spirit or scope ofthe disclosure or from the scope of the following claims.

I claim:

1. N-polyhalovinylthiocarboxamide of the formula wherein R is alkyl ofone to 10 carbon atoms, alkenyl of two to 10 carbon atoms, alkynyl oftwo to 10 carbon atoms, haloalkyl of one to 10 carbon atoms and one tothree halogen atoms of atomic number 17 to 35, cycloalkyl of three to 10carbon atoms, cycloalkyl of three to 10 carbon atoms substituted withone to three halogen atoms of atomic number 17 to 35, or

cycloalkenyl of three to 10 carbon atoms, R is hydrogen or alkyl of oneto four carbon atoms with the proviso that R and R may be joined to forma linear alkylene radical of three to five carbon atoms which is boundto the carbonyl and nitrogen to form a ring, X is halogen of atomicnumber 17 to 35 and a is two or three.

2. The carboxamide of claim 1 wherein X is chlorine and a is three.

3. The carboxamide of claim 1 wherein R is alkyl of one to eight carbonatoms, haloalkyl of one to eight carbon atoms and one to three halogenatoms of atomic number 17 to 35, cycloalkyl of three to eight carbonatoms or cycloalkyl of three to eight carbon atoms substituted with oneto three halogen atoms of atomic number 17 to 35.

4. The carboxamide of claim 3 wherein R is alkyl of one to eight carbonatoms, haloalkyl of one to eight carbon atoms and one to two chlorineatoms, cycloalkyl of three to eight carbon atoms or cycloalkyl of threeto eight carbon atoms subtituted with one to two chlorine atoms.

5. The carboxamide of claim 1 wherein X is chlorine, a is three, R ismethyl and R is hydrogen.

6. The carboxamide of claim 1 wherein X is chlorine, a is three, R and Rare joined to form a linear pro yl ene or amylene radical which is boundto the carbonyl an nitrogen to form a ring.

7. N-polyhalovinylthiocarboxamide of the formula wherein R is alkyl ofone to l carbon atoms, alkenyl of two to l0 carbon atoms, haloalkyl ofone to ID carbon atoms and one to three halogen atoms of atomic numberI? to 35, propynyl, cycloalkyl of three to eight carbon atoms,cyclohexyl substituted with one to three halogen atoms of atomic number17 to 35, R is hydrogen or alkyl of one to four carbon atoms, X ishalogen of atomic number 17 to 35 and a is two or three.

8. The carboxamide of claim 7 wherein X is chlorine, R is

2. The carboxamide of claim 1 wherein X is chlorine and a is three. 3.The carboxamide of claim 1 wherein R is alkyl of one to eight carbonatoms, haloalkyl of one to eight carbon atoms and one to three halogenatoms of atomic number 17 to 35, cycloalkyl of three to eight carbonatoms or cycloalkyl of three to eight carbon atoms substituted with oneto three halogen atoms of atomic number 17 to
 35. 4. The carboxamide ofclaim 3 wherein R is alkyl of one to eight carbon atoms, haloalkyl ofone to eight carbon atoms and one to two chlorine atoms, cycloalkyl ofthree to eight carbon atoms or cycloalkyl of three to eight carbon atomssubtituted with one to two chlorine atoms.
 5. The carboxamide of claim 1wherein X is chlorine, a is three, R is methyl and R'' is hydrogen. 6.The carboxamide of claim 1 wherein X is chlorine, a is three, R and R''are joined to form a linear propylene or amylene radical which is boundto the carbonyl and nitrogen to form a ring. 7.N-polyhalovinylthiocarboxamide of the formula wherein R is alkyl of oneto 10 carbon atoms, alkenyl of two to 10 carbon atoms, haloalkyl of oneto 10 carbon atoms and one to three halogen atoms of atomic number 17 to35, propynyl, cycloalkyl of three to eight carbon atoms, cyclohexylsubstituted with one to three halogen atoms of atomic number 17 to 35,R'' is hydrogen or alkyl of one to four carbon atoms, X is halogen ofatomic number 17 to 35 and a is two or three.
 8. The carboxamide ofclaim 7 wherein X is chlorine, R is alkyl of one to eight carbon atoms,alkenyl of two to eight carbon atoms or chloroalkyl of one to eightcarbon atoms and one or two chlorine atoms and R'' is hydrogen. 9.Compound of claim 7 wherein R is alkyl of one to eight carbon atoms,chloromethyl, bromomethyl, cycloalkyl of three to six carbon atoms, R''is hydrogen or methyl and X is chlorine.